CN102341369B - For the preparation of the method and apparatus of isocyanic ester - Google Patents
For the preparation of the method and apparatus of isocyanic ester Download PDFInfo
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- CN102341369B CN102341369B CN201080010251.8A CN201080010251A CN102341369B CN 102341369 B CN102341369 B CN 102341369B CN 201080010251 A CN201080010251 A CN 201080010251A CN 102341369 B CN102341369 B CN 102341369B
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- isocyanic ester
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- 150000002148 esters Chemical class 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 119
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000006200 vaporizer Substances 0.000 claims abstract description 16
- 230000008859 change Effects 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 43
- 238000010791 quenching Methods 0.000 claims description 28
- 230000000171 quenching effect Effects 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 25
- 238000009833 condensation Methods 0.000 claims description 16
- 230000005494 condensation Effects 0.000 claims description 16
- 239000012495 reaction gas Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 claims description 5
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 5
- 238000005485 electric heating Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 235000011089 carbon dioxide Nutrition 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 230000003746 surface roughness Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 16
- -1 Alicyclic isocyanate Chemical class 0.000 description 14
- 230000008020 evaporation Effects 0.000 description 8
- 239000008246 gaseous mixture Substances 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- MKZPMOFOBNHBSL-UHFFFAOYSA-N 1-isocyanato-1-methylcyclohexane Chemical compound O=C=NC1(C)CCCCC1 MKZPMOFOBNHBSL-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical compound NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical class O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ODKSRULWLOLNJQ-UHFFFAOYSA-N 1,2-diisocyanatocyclohexane Chemical compound O=C=NC1CCCCC1N=C=O ODKSRULWLOLNJQ-UHFFFAOYSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 1
- OHTRJOZKRSVAOX-UHFFFAOYSA-N 1,3-diisocyanato-2-methylcyclohexane Chemical compound CC1C(N=C=O)CCCC1N=C=O OHTRJOZKRSVAOX-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical group CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CVGYTOLNWAMTRJ-UHFFFAOYSA-N N=C=O.N=C=O.CCCCC(C)C(C)(C)C Chemical compound N=C=O.N=C=O.CCCCC(C)C(C)(C)C CVGYTOLNWAMTRJ-UHFFFAOYSA-N 0.000 description 1
- JTDWCIXOEPQECG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC(C)(C)C Chemical compound N=C=O.N=C=O.CCCCCC(C)(C)C JTDWCIXOEPQECG-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical class CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical class COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000178 monomer Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/10—Mixing by creating a vortex flow, e.g. by tangential introduction of flow components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/30—Injector mixers
- B01F25/31—Injector mixers in conduits or tubes through which the main component flows
- B01F25/313—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit
- B01F25/3131—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit with additional mixing means other than injector mixers, e.g. screens, baffles or rotating elements
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/18—Separation; Purification; Stabilisation; Use of additives
- C07C263/20—Separation; Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of method for the preparation of isocyanic ester, optionally react in the presence of an inert media in the gas phase by making corresponding amine and phosgene and carry out, described amine is wherein made to evaporate to obtain the air-flow containing amine in vaporizer, phosgene being mixed into this contains in the air-flow of amine, and making described amine photoreactive gas change into isocyanic ester in the reactor, the dew point wherein making the temperature on the surface contacted with gaseous state amine remain on higher than the air-flow containing amine is limit.The invention still further relates to a kind of device for the preparation of isocyanic ester, preparation process is reacted in the gas phase by making corresponding amine and phosgene and is carried out, described device comprises one is implemented reaction reactor for the vaporizer and evaporating amine, and the coupling device of vaporizer and reactor, wherein the surface that may come in contact with gaseous state amine is provided and can not be soaked by amine, according to DIN? ISO? the average surface roughness Rz of 4287 coating of 10 μm at the most, and/or described device does not have dead band and does not have heat bridge.
Description
The present invention relates to a kind of method for the preparation of isocyanic ester, optionally react in the presence of an inert media in the gas phase by making corresponding amine and phosgene and carry out, wherein evaporated in vaporizer by described amine and mix with phosgene, described amine photoreactive gas changes into isocyanic ester in the reactor.
Prepare isocyanic ester by the corresponding amine of phosgenation to realize by liquid phase or gas phase phosgenation in principle.The feature of gas phase phosgenation is higher selectivity, lower poisonous phosgene hold-up (holdup), and required energy is lower.
In gas phase phosgenation, the reactant flow containing amine and the reactant flow containing phosgene are mixed with gaseous state separately.Described amine photoreactive gas reaction, discharges hydrogenchloride (HCl), generates corresponding isocyanic ester.Reactant flow containing amine is present in liquid phase usually, and it must be made before mixing with the reactant flow containing phosgene to evaporate and optionally overheated.
The correlation method preparing isocyanic ester in the gas phase has description in such as EP-A1319655, EP-A1555258, EP-A1935876 or EP-A0289840.
In order to mixing contains the reactant flow of amine and the reactant flow containing phosgene in the gas phase, need first to evaporate this reactant flow containing amine.Suitable vaporizer has open in such as EP-A1754698.
But a shortcoming for the currently known methods of gas phase phosgenation forms solid deposits between vaporizer and mixed cell, and this makes to need cleaning system.Cause the reason of this point be with the surface that contacts of amine of evaporation in local or whole region its temperature lower than the dew-point temperature of gaseous mixture.Amine condensation on these surfaces, the cracking gradually (crack) due to the longer residence time and higher temperature, thus form settling from the teeth outwards.These settlings may increase and form tectum or cause upstream device parts due to entrained solids component---as mixing nozzle---obstruction.Therefore periodic cleaning is needed.Need closing device for this reason.By condensation and the settling that formed of the amine of cracking such as may in the upper and lower play pipe road of the wall of vaporizer and device---such as droplet separator or heat transmitter---be upper produces.
On amine supply line internal surface, temperature has the thermosteresis in such as pipeline and device lower than the reason that dew point is limit, or the adding of colder gaseous inert air-flow.Especially close to heat bridge place with in the dead band of air-flow, the risk that condensation product is formed is large especially.The dead band of air-flow such as can produce due to metering orifice (such as pressure survey or temperature survey) or due to control unit as cock or valve.But, on a rough surface or the formation of crack or slight crack place solid deposits also can increase.
Therefore an object of the present invention is to provide a kind of method for the preparation of isocyanic ester, the method is undertaken by making corresponding amine and phosgene reaction in the gas phase, can prevent from blocking to mixed cell at amine supply line by the method, described obstruction needs carry out cleaning and therefore need equipment is stopped.
This object is realized by a kind of method for the preparation of isocyanic ester, the method is optionally reacted in the presence of an inert media in the gas phase by making corresponding amine and phosgene and is carried out, described amine is wherein made to evaporate to obtain the air-flow containing amine in vaporizer, phosgene being mixed into this contains in the air-flow of amine, and making described amine photoreactive gas change into isocyanic ester in the reactor, the dew point wherein making the temperature on the surface contacted with gaseous state amine remain on higher than the air-flow containing amine is limit.
The surface contacted with gaseous state amine is, such as, for the surface by making corresponding amine and phosgene reaction prepare pipeline in the device of isocyanic ester, assembly and device.The device used is, such as mixed cell, heat transmitter or reactor; Assembly is, such as valve, cock or measurement and control unit.
The appropriate method keeping the temperature on surface that contacts with gaseous state amine to limit higher than the dew point of the air-flow containing amine is, such as:
A () is crossed the logistics of hot gaseous amine and is down to below dew point to get rid of the local caused by thermosteresis,
(b) make pipeline and device heat insulation to make further minimum heat losses,
C () water back and device are down to below dew point to prevent local,
D () passes into the inert gas of control temperature to improve the dew point of the gaseous mixture containing amine.
Aforesaid method can be implemented separately or implement with two or more arbitrary combination.
Method of the present invention prevents or significantly reduces for the preparation of the sedimental formation on the appts wall of isocyanic ester.
In addition, solid deposits also prevents by structural approach or reduces.
Amine is interpreted as dew point limit or the dew-point temperature of the air-flow containing amine respectively from the temperature gone out containing condensation the air-flow of amine at a given pressure.
A reactor implementing to react for the vaporizer and one that evaporate amine is comprised by the appropriate device making corresponding amine and phosgene reaction prepare isocyanic ester in the gas phase, and the coupling device of described vaporizer and reactor.According to the present invention, the surface that may come in contact with gaseous state amine provides and can not be soaked by amine and be not more than the coating of 10 μm according to the mean roughness degree of depth Rz of DINISO4287, and/or described device does not have dead band or heat bridge.Use device of the present invention can prevent from forming settling on the apparatus assembly that may come in contact with gaseous state amine, such as on the surface of amine vaporizer, connect vaporizer on the pipeline of reactor and the surface of reactor.
When making amine passes through heat can prevent there is thermosteresis, temperature is reduced to below dew-point temperature.If carry out suitable design, overheatedly can to complete in vaporizer.But, due to the thermolysis of at high temperature amine, preferably make the overheated of amine logistics minimize.Pipeline and the heat insulation of device make further minimum heat losses, thus make necessary overheated remain on less.Find that the favourable temperature difference limit with condensation is at least 5K, is preferably at least 10K and is more preferably at least 20K.This especially can prevent local temperature to be reduced to below condensation limit, especially at heat bridge or flow dead place.
Prevent from the surface contacted with gaseous state amine, occur that another very effective method of condensation product carries out accompanying heat to guarantee that the surface temperature on the surface contacted with gaseous state amine is higher than dew-point temperature to device and pipeline.Can prevent in this way or even compensate thermosteresis.Adjustment companion heat limits at least 5K, preferably at least 10K and the surface temperature of more preferably at least 20K to be formed higher than condensation.Companion's heat on surface is such as had the wall of chuck by design or uses coiled pipe heating medium is flow through or is realized by electrically heated.
The rare gas element of control temperature is passed in amine logistics and make the dividing potential drop of amine reduce and make the dew point of gaseous mixture also reduce thus.The inert media used can be, such as nitrogen, rare gas element such as helium or argon gas, and aromatics is chlorobenzene, orthodichlorobenzene, trichlorine benzene,toluene,xylene, chloronaphthalene, naphthalane such as, carbonic acid gas, carbon monoxide, and composition thereof.Preferred use nitrogen and/or chlorobenzene.The temperature of rare gas element of adjustment supply makes mixing temperature and condensation limit to exist at least 5K, preferred at least 10K and the temperature head of more preferably at least 20K.
Compared with means known in the art, prevent forming settling by the inventive method and make for the preparation of increasing the work-ing life of the equipment of isocyanic ester.Do not need to stop frequently with cleaning equipment.
In order to prepare isocyanic ester, first phosgene and amine are preferably fed mixing region, amine photoreactive gas is obtained by mixing reaction mixture in this region.Subsequently, this reaction mixture is supplied in reactor, realizes the conversion to isocyanic ester wherein.The conversion in the reactor of amine photoreactive gas is carried out in the gas phase.For this reason, the absolute pressure in reactor preferably in 0.3 to 5bar scope, more preferably in 0.8 to 3.5bar scope.Temperature preferably within the scope of 250 to 550 DEG C, particularly within the scope of 300 to 500 DEG C.
In order to this reaction can be implemented in the gas phase, amine photoreactive gas is added in a gaseous form.For this reason, the temperature of described amine is preferably within the scope of 200 to 400 DEG C.The absolute pressure of the amine added is preferably in 0.05 to 3bar scope.The temperature of the phosgene added is preferably within the scope of 250 to 500 DEG C.For this reason, usually phosgene is heated with method known to those skilled in the art before addition.
In order to heat phosgene and amine and in order to evaporate amine, use such as electrically heated or directly or indirectly being heated by fuel combustion.The fuel used is generally combustion gas, such as Sweet natural gas.But because pressure in evaporative process reduces, thus making the boiling temperature of amine reduce, is also feasible by steam heating.The pressure of steam is selected according to the boiling temperature of amine herein.The suitable vapor pressure of steam is such as in 40 to 100bar scope.It causes the temperature of steam within the scope of 250 to 311 DEG C.
Usually, need to heat amine in multiple steps to temperature of reaction.In order to this object, usually first by amine preheating, then evaporate, and then overheated.Usually, evaporation occupies the longest residence time and therefore causes the decomposition of amine.In order to make the decomposition of amine minimize, the evaporation at lower temperatures such as produced by lower pressure is favourable.In order to after evaporation the amine of evaporation is superheated to temperature of reaction, normally inadequate by steam heating.Therefore in order to overheated, usually use electrically heated or directly or indirectly heated by fuel combustion.
Due to amine high boiling temperature and cause with the larger temperature difference of environment, the temperature of the wall of equipment unit (such as connecting the pipeline of vaporizer and reactor) or reactor parts (such as supply line or supplying-nozzle) may lower than the vaporization temperature of amine.This causes amine to be condensed on wall from air-flow.The drop of condensation to be attached on wall and to cause solid and sedimental formation due to high temperature.Described settling such as reduces cross-section of pipeline, and in some cases, for very little diameter, cross-section of pipeline may be totally blocked.This makes to need periodic cleaning equipment unit.Method of the present invention reduces or prevents described sedimental formation, thus can obtain longer service life of equipment.
Formed with the evaporation of amine and contrast, phosgene evaporates usually at significantly lower temperature.For this reason, usually steam raising phosgene can be used.But, in order to phosgene is heated to temperature of reaction and to phosgene carry out necessary overheated usually also can only by electrically heated or directly or indirectly heated by fuel combustion and carry out.
The reactor that isocyanic ester is prepared in phosgenation for amine is known to the person skilled in the art.Usually, the reactor of use is tubular reactor.In the reactor, amine and phosgene reaction obtain corresponding isocyanic ester and hydrogenchloride.Usually, add excessive for phosgene, make the reaction gas formed in the reactor, except formed isocyanic ester and hydrogenchloride except, also comprise phosgene.
The amine that can be used for preparing isocyanic ester is monoamine, diamine, tertiary amine or higher functional degree amine.Preferred use monoamine or diamine.According to the amine used, obtain corresponding monoisocyanates, vulcabond, triisocyanate or higher functional degree isocyanic ester.Monoisocyanates or vulcabond is prepared preferably by the inventive method.
Diamine and vulcabond can be aliphatic, alicyclic (cycloaliphatic) or aromatics.
Alicyclic isocyanate is the isocyanic ester comprising at least one alicyclic ring system.
Aliphatic isocyanate is the isocyanic ester only with the isocyanate groups being bonded to straight or branched.
Aromatic isocyanate has the isocyanic ester that at least one is bonded to the isocyanate groups of at least one aromatic ring system.
Term " fat (ring) race isocyanic ester " is hereafter for alicyclic and/or aliphatic isocyanate.
The monoisocyanates of aromatics and the example of vulcabond are preferably containing those of 6 to 20 carbon atoms, such as phenylcarbimide, monomer class 2,4 '-and/or 4,4 '-methylene radical-two (phenylcarbimide) (MDI), 2,4-and/or 2,6-tolylene diisocyanate (TDI) and 1,5-or 1,8-naphthalene diisocyanate (NDI).
The example of fat (ring) (cyclo) aliphatic diisocyanates is aliphatic vulcabond, such as 1, 4-tetramethylene diisocyanate, 1, 6-hexamethylene diisocyanate (1, 6-bis-isocyanato-hexane), 1, 8-eight methylene diisocyanate, 1, 10-decamethylene vulcabond, 1, 12-ten dimethylene diisocyanate, 1, 14-ten tetramethylene diisocyanate, 1, 5-bis-isocyanato-pentane, neopentane vulcabond, lysinediisocyanate derivative, tetramethyl xylylen vulcabond (TMXDI), trimethylhexane diisocyanate or tetramethylhexane diisocyanate, and 3 (or 4), 8 (or 9)-two (isocyanatomethyl) three ring [5.2.1.0
2,6] decane isomer mixture, with alicyclic diisocyanate as 1,4-, 1,3-or 1,2-bis-isocyanatocyclohexane, 4,4 '-or 2,4 '-two (isocyanatocyclohexyl) methane, 1-isocyanato--3,3,5-trimethylammonium-5-(isocyanatomethyl) hexanaphthene (isophorone diisocyanate), 1,3-or 1,4-bis-(isocyanatomethyl) hexanaphthene, 2,4-or 2,6-bis-isocyanato--1-methylcyclohexane.
Preferred fat (ring) (cyclo) aliphatic diisocyanates is 1,6-bis-isocyanato-hexane, 1-isocyanato--3,3,5-trimethylammonium-5-(isocyanatomethyl) hexanaphthene and 4,4 '-two (isocyanatocyclohexyl) methane.Particularly preferably 1,6-bis-isocyanato-hexane, 1-isocyanato--3,3,5-trimethylammonium-5-(isocyanatomethyl) hexanaphthene and 4,4 '-two (isocyanatocyclohexyl) methane.
The amine obtaining corresponding isocyanic ester in the inventive method for reacting is such amine: described amine, corresponding intermediate and corresponding isocyanic ester exist in a gaseous form under selected reaction conditions.The degree of preferably during reaction decomposing at reaction conditions mostly is most 2mol%, mostly more preferably most is 1mol% and mostly most preferably is most the amine of 0.5mol%.Here specially suitable amine is especially based on the diamine of fat (ring) race hydrocarbon with 2 to 18 carbon atoms.The example has 1，6-diaminohexane, 1,5-1,5-DAP, 1,3-bis-(amino methyl) hexanaphthene, amino-3,3,5-trimethylammonium-5-aminomethyl cyclohexane (IPDA) of 1-and 4,4-diamino-dicyclohexyl methane.Preferred use 1，6-diaminohexane (HDA).
For method of the present invention, the aromatic amine that can change into gas phase and obviously decomposition also can be used.The example of preferred aromatic amine has tolylene diamine (TDA), such as with 2,4 or 2,6 isomer or its form of mixtures, the such as mixture of 80:20 to 65:35 (mol/mol), diaminobenzene, 2,6-xylidine, naphthylene diamine (NDA) and 2,4 '-or 4,4 '-methylene radical (diphenyl diamine) (MDA), or its isomer mixture.Wherein preferred diamines, particularly preferably 2,4-and/or 2,6-TDA or 2,4 '-and/or 4,4 '-MDA.
In order to prepare monoisocyanates, also can use aliphatic series, alicyclic or aromatic amine, being generally monoamine.Preferred aromatic monoamine especially aniline.
In gas phase phosgenation, the compound desirably existed in reaction process, namely reactant (amine photoreactive gas), intermediate (the carbamyl hydrochloride especially formed as intermediate and amine hydrochloride), end product (vulcabond) and any inert compound of being metered into, keep in the gas phase at reaction conditions.Just in case these or other component is deposited on such as reactor wall or other device assemblies from gas phase, these settlings adversely may change heat transfer or the flowing through affected components.Especially true when the amine hydrochloride formed by free amine group and hydrogenchloride exists, because the amine hydrochloride obtained easily precipitates and reevaporates difficulty.
Except using tubular reactor, also can use substantially cuboidal reaction chamber, such as plate-type reactor.Reactor can have different cross section required arbitrarily.
In order to prevent the formation of by product in reaction, preferred glut phosgene.In order to the amine of only ratio needed for supply response, can by amine and rare gas element mixing.The amount of the amine that the amine photoreactive gas opening for feed place that in useful amine, the ratio of rare gas element adjusts given geometrical shape supplies.Addible inert media is the material existing in a gaseous form in the reaction chamber and do not react with the compound existed in reaction process.The inert media used can be that such as nitrogen, rare gas element such as helium or argon gas, aromatics is chlorobenzene, orthodichlorobenzene, trichlorine benzene,toluene,xylene, chloronaphthalene, naphthalane, carbonic acid gas or carbon monoxide such as.But, preferably use nitrogen and/or chlorobenzene as inert media.
But on the other hand, such as, in order to avoid phosgene is too much excessive, also inert media can be added in phosgene.
Usually, the add-on of inert media is make inert media and amine or be less than 0.0001 to 30 with the ratio of the gas volume of phosgene, is preferably less than 0.01 to 15 and is more preferably less than 0.1 to 5.
The suitable coating of the amine attachment that can prevent condensation from going out has, such as, comprise SiO
xcoating, such as purchased from the Silcosteel coating of RestecCorporation.
When preventing amine in respective surfaces during condensation by heating surface, at least 5K is limit in the condensation of the gaseous mixture that the temperature on the surface that may come in contact with amine is preferably heated above containing amine, more preferably at least 10K, especially at least 15K.This condensation limit is measured by inert gas content in the pressure in amine pipeline and gaseous mixture.
Such as when the ratio increase of amine in air-flow or when running under relatively high pressure for the preparation of the device of isocyanic ester, the temperature that the surface similarly also needing increase may come in contact with amine is heated to.
Described surface is by any heating means heating well known by persons skilled in the art.Preferred use an electric heating element heating surface.The advantage using an electric heating element is that it can be set to assigned temperature in a simple manner.
In order to reduce or prevent the formation of less desirable by product, and in order to suppress the decomposition of the isocyanic ester formed, preferably in expander, cool reaction gas immediately after the reaction.For this reason, the quenching medium being generally liquid is added.Due to the evaporation of quenching medium, it absorbs heat and causes the rapid cooling of reaction gas.Adding of quenching medium causes the mixture of reaction gas and quenching medium to become product stream.
Rapid cooling realizes particularly by the quenching medium adding form of fine mist.Therefore, described quenching medium has large surface-area and promptly can absorb heat and cool reaction gas thus.
According to the present invention, described quenching medium adds with the liquid form of temperature higher than reaction gas condensing temperature.In order to prevent the premature evaporation of quenching medium, may need to increase the pressure in feeding line compared with the pressure in quenching space.The pressure in quenching space is depressed into afterwards by nozzle itself or other suitable control unit solutions.The decompression of quenching medium and with the mixing the heating that realizes quenching medium and/or partially or completely evaporate of thermal response gas.The heat absorbed in this process causes the cooling of reaction gas.
Especially, when being used in quenching medium lower than reaction gas condensing temperature of boiling temperature under the condition in quenching space, pressure in feeding line is improved to prevent quenching medium at the front evaporator adding quenching space compared with the pressure in quenching space.
Quenching medium adds fashionable pressure preferably in 1 to 20bar scope, more preferably in 1 to 10bar scope, especially in 1 to 8bar scope.
Quenching medium for cooling preferably includes and is a kind ofly selected from following solvent: monochloro benzene, dichlorobenzene, trichlorobenzene, hexane, benzene, 1,3,5-Three methyl Benzene, oil of mirbane, methyl-phenoxide, toluene(mono)chloride, orthodichlorobenzene, m-phthalic acid diethyl ester, tetrahydrofuran (THF), dimethyl formamide, dimethylbenzene, chloronaphthalene, naphthalane and toluene.
In one embodiment of the invention, other steps can be carried out after quenching to cool reaction gas.In each step for cooling, separately reaction gas being cooled further, until reach required outlet temperature, at such a temperature reaction gas being delivered to such as downstream and carrying out aftertreatment.
In one embodiment, at least one is further quenching for cooling the step of reaction gas after the quenching.
Such as, preferably at the temperature more than 130 DEG C, the reaction gas of quenching and cooling step possible thereafter can be left with solvent wash.Suitable solvent has, such as, also can be used as the same substance of quenching medium.
In washing process, transfer in washing soln selective isocyanate.Next, residual gas is become isocyanic ester, solvent, phosgene and hydrogenchloride with the washing soln of generation preferably by rectifying separation.
The gaseous mixture leaving reactor preferably washs in scrubbing tower, from the gaseous mixture of gaseous state, the isocyanic ester of formation is shifted out, if simultaneously excessive phosgene, hydrogenchloride and suitable inert medium are in a gaseous form through after-treatment device by condensation in inert solvent.The temperature of preferred maintenance inert solvent is higher than the solvent temperature of the urea chloride corresponding to described amine in selected washing medium.The temperature of inert solvent more preferably remains on the temperature of fusion higher than the urea chloride corresponding to described amine.
Washing can be carried out in required device arbitrarily well known by persons skilled in the art.Such as, stirred vessel or other conventional equipments are all suitable, such as tower or mixing tank-precipitator device.
The reaction gas leaving reactor carries out washing and aftertreatment usually as described in WO-A2007/028715.
As previously discussed, coating preferably includes SiO
x.
In a further preferred embodiment, the device for heating the surface that may come in contact with gaseous state amine is also comprised.For heating the appropriate device especially an electric heating element on described surface.But, use the embodiment with the sheathed heater of corresponding heating medium to be also feasible.The surface that may come in contact with gaseous state amine has, the surface of such as vaporizer and reactor, and the tube wall that gaseous state amine flows through.Use for the device of heating surface makes the condensing temperature that surface temperature can be kept higher than the gaseous mixture containing amine, can prevent amine condensation from going out thus.It also prevents from forming throw out from the teeth outwards.
Claims (9)
1. the method for the preparation of isocyanic ester, optionally react in the presence of an inert media in the gas phase by making corresponding amine and phosgene and carry out, described amine is wherein made to evaporate to obtain the air-flow containing amine in vaporizer, phosgene being mixed into this contains in the air-flow of amine, and make described amine photoreactive gas change into isocyanic ester in the reactor, wherein, the dew point that the temperature on the surface contacted with gaseous state amine is remained on higher than the air-flow containing amine is limit, wherein by making pipeline and the heat insulation dew point making the temperature on the surface contacted with gaseous state amine remain on higher than the air-flow containing amine to make further minimum heat losses and realize at least one following characteristics of device limit:
A () is crossed the logistics of hot gaseous amine and is down to below dew point to get rid of the local caused by thermosteresis,
B () water back and device are down to below dew point to prevent local,
(c) supply inert gas, wherein the temperature of rare gas element is adjusted to and makes mixing temperature limit with the condensation of the air-flow containing amine the temperature head that there is at least 5K;
Described rare gas element is the gas existing in the reaction chamber and do not react with the compound existed in reaction process.
2. method according to claim 1, the temperature that the surface wherein come in contact with described amine is heated to is the condensing temperature at least 5K higher than the air-flow containing amine.
3. method according to claim 1, wherein said surface uses an electric heating element or sheathed heater heating.
4. method according to claim 2, wherein said surface uses an electric heating element or sheathed heater heating.
5. method according to claim 1, the temperature head that the mixing temperature that the inert gas wherein passing into control temperature produces at least 5K is limit with the condensation of the air-flow containing amine.
6. method according to claim 1, the rare gas element wherein used is nitrogen, helium, argon gas, chlorobenzene, orthodichlorobenzene, toluene, dimethylbenzene, chloronaphthalene, naphthalane, carbonic acid gas, carbon monoxide or its mixture.
7. method according to claim 1, wherein will comprise isocyanic ester and hydrogenchloride and the reaction gas leaving reactor is cooled by adding liquid quenching medium at expander, and the mixture of forming reactions gas and quenching medium is as product stream.
8. method according to claim 7, wherein said quenching medium comprises and is a kind ofly selected from following solvent: monochloro benzene, dichlorobenzene, trichlorobenzene, hexane, benzene, 1,3,5-Three methyl Benzene, oil of mirbane, methyl-phenoxide, toluene(mono)chloride, m-phthalic acid diethyl ester, tetrahydrofuran (THF), dimethyl formamide, dimethylbenzene, chloronaphthalene, naphthalane and toluene.
9. method according to claim 7, wherein carries out other steps and carrys out after-treatment products stream after described quenching.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09154490.8 | 2009-03-06 | ||
| EP09154490 | 2009-03-06 | ||
| PCT/EP2010/052748 WO2010100221A1 (en) | 2009-03-06 | 2010-03-04 | Method and device for producing isocyanates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102341369A CN102341369A (en) | 2012-02-01 |
| CN102341369B true CN102341369B (en) | 2015-11-25 |
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| CN201080010251.8A Active CN102341369B (en) | 2009-03-06 | 2010-03-04 | For the preparation of the method and apparatus of isocyanic ester |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20110301380A1 (en) |
| EP (1) | EP2403826B1 (en) |
| JP (1) | JP5771535B2 (en) |
| KR (1) | KR20110135937A (en) |
| CN (1) | CN102341369B (en) |
| WO (1) | WO2010100221A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010106131A2 (en) * | 2009-03-20 | 2010-09-23 | Basf Se | Method and device for producing isocyanates |
| DE102009033639A1 (en) * | 2009-07-17 | 2011-01-20 | Bayer Materialscience Ag | Procedures for the preparation of isocyanates in the gas phase |
| US8716517B2 (en) | 2009-08-11 | 2014-05-06 | Basf Se | Method for producing diisocyanates by gas-phase phosgenation |
| PT2507206E (en) | 2009-12-04 | 2014-12-26 | Basf Se | Method for producing isocyanates |
| US8981145B2 (en) | 2010-03-18 | 2015-03-17 | Basf Se | Process for preparing isocyanates |
| US9321720B2 (en) | 2010-10-14 | 2016-04-26 | Basf Se | Process for preparing isocyanates |
| EP2829533A1 (en) * | 2013-07-26 | 2015-01-28 | Bayer MaterialScience AG | Method for making isocyanates |
| HUE037053T2 (en) * | 2014-03-27 | 2018-08-28 | Covestro Deutschland Ag | Method for manufacturing isocyanates |
| KR20160138410A (en) * | 2014-03-27 | 2016-12-05 | 코베스트로 도이칠란트 아게 | Method for operating a gas-phase phosgenation plant |
| WO2015144682A1 (en) * | 2014-03-27 | 2015-10-01 | Bayer Material Science Ag | Process for operating a gas phase phosgenation plant |
| CN114195683B (en) * | 2021-12-14 | 2023-03-17 | 山东新和成维生素有限公司 | Method for preparing isocyanate by adopting gas phase reactor and gas phase reactor |
| CN115286535B (en) * | 2022-08-17 | 2023-10-17 | 万华化学集团股份有限公司 | Isocyanate preparation process and salifying and photochemical reaction coupling device |
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| CN1907964A (en) * | 2005-08-02 | 2007-02-07 | 拜尔材料科学股份公司 | Gas phase phosgenation process |
| WO2008055899A1 (en) * | 2006-11-07 | 2008-05-15 | Basf Se | Method for producing isocyanates |
| WO2008071564A1 (en) * | 2006-12-11 | 2008-06-19 | Basf Se | Process for preparing isocyanates |
| CN101205197A (en) * | 2006-12-13 | 2008-06-25 | 拜尔材料科学股份公司 | Method for producing isocyanates in the gas phase |
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| DE3714439A1 (en) | 1987-04-30 | 1988-11-10 | Bayer Ag | METHOD FOR PRODUCING (CYCLO) ALIPHATIC DIISOCYANATES |
| JP3782607B2 (en) * | 1999-04-20 | 2006-06-07 | 株式会社日本触媒 | Method for producing esterified product |
| JP2000344688A (en) * | 1999-06-04 | 2000-12-12 | Mitsubishi Chemicals Corp | Purification of readily polymerizable compound |
| DE10161384A1 (en) | 2001-12-14 | 2003-06-18 | Bayer Ag | Improved process for the production of (/ poly) -isocyanates in the gas phase |
| JP4325146B2 (en) * | 2002-03-11 | 2009-09-02 | 三菱化学株式会社 | Method for producing (meth) acrylic acids |
| DE10220494A1 (en) * | 2002-05-07 | 2003-11-20 | Basf Ag | Process for the preparation of an aqueous alkali acrylate solution |
| DE10359627A1 (en) | 2003-12-18 | 2005-07-21 | Bayer Materialscience Ag | Process for the preparation of diisocyanates |
| DE102005042392A1 (en) | 2005-09-06 | 2007-03-08 | Basf Ag | Process for the preparation of isocyanates |
| DE102006058634A1 (en) * | 2006-12-13 | 2008-06-19 | Bayer Materialscience Ag | Producing isocyanates comprises reacting phosgene and amines, cooling the obtained gas mixture for the condensation of formed isocyanate and separating the non-condensed isocyanate from the mixture by washing |
-
2010
- 2010-03-04 KR KR1020117021079A patent/KR20110135937A/en not_active Application Discontinuation
- 2010-03-04 US US13/202,175 patent/US20110301380A1/en not_active Abandoned
- 2010-03-04 EP EP10706260.6A patent/EP2403826B1/en active Active
- 2010-03-04 JP JP2011552446A patent/JP5771535B2/en not_active Expired - Fee Related
- 2010-03-04 CN CN201080010251.8A patent/CN102341369B/en active Active
- 2010-03-04 WO PCT/EP2010/052748 patent/WO2010100221A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1907964A (en) * | 2005-08-02 | 2007-02-07 | 拜尔材料科学股份公司 | Gas phase phosgenation process |
| WO2008055899A1 (en) * | 2006-11-07 | 2008-05-15 | Basf Se | Method for producing isocyanates |
| WO2008071564A1 (en) * | 2006-12-11 | 2008-06-19 | Basf Se | Process for preparing isocyanates |
| CN101205197A (en) * | 2006-12-13 | 2008-06-25 | 拜尔材料科学股份公司 | Method for producing isocyanates in the gas phase |
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| JP2012519667A (en) | 2012-08-30 |
| CN102341369A (en) | 2012-02-01 |
| JP5771535B2 (en) | 2015-09-02 |
| WO2010100221A1 (en) | 2010-09-10 |
| US20110301380A1 (en) | 2011-12-08 |
| EP2403826A1 (en) | 2012-01-11 |
| EP2403826B1 (en) | 2017-05-24 |
| KR20110135937A (en) | 2011-12-20 |
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